A field day: The large π-conjugated N-heteroquinone 6,10,17,21-tetra[(triisopropylsilyl)ethynyl]-5,7,9,11,16,18,20,22-octaazanonacene-8,19-dione (OANQ; see Figure) has been successfully synthesized and characterized. A field-effect transistor device based on OANQ single crystals displays an electron mobility of up to 0.2 cm2 V−1 s−1 under ambient conditions.

On the dot: A facile approach to photoluminescent carbon dots (CDs) that can be excited by a single wavelength and demonstrate emission of the three primary colors (red, green, and blue) is reported. The resulting CDs can be potentially used in the fabrication of flexible full-color emission films and in multicolor cellular imaging.

Framed: The title frameworks were fabricated from self-assembled Fe3O4 nanocrystal superlattices. Because of their unique architectures and superior structure durability, the mesoporous graphene frameworks exhibit excellent electrochemical performance when used as anode materials for lithium-ion batteries.

Keeping score: Nucleic acid sequences and sequence counts were used as multivariate data without the necessity of a spatial array. Aptamers were used as semi-specific receptors for cell line differentiation, and cross-reactivity between the aptamers was observed. The principal component analysis (PCA) generates high-dimensionality score plots, thus differentiating a mixture of complex and subtly different analytes.

A novel general strategy was used for precise distance measurements on an outer membrane protein in whole E. coli cells and isolated outer membranes. This approach provides an elegant way to study conformational changes or protein–protein/ligand interactions under native conditions and provides a method to validate high-resolution structures of membrane proteins in their native environment.

1+1=3: By combining the exceptional reactivities of cyclic hypervalent iodine reagents and iron catalysts, Sharma and Hartwig achieved the azidation of CH bonds with unprecedented efficiency and selectivity. The late-stage introduction of azides into complex bioactive molecules will greatly facilitate the synthesis of analogues and accelerate the discovery of new chemical entities.

Selective laser sintering has been used to prepare synthetic materials from a new type of self-immolative polymer. These materials autonomously amplify macroscopic and nonlocalized changes in the material in response to specific molecular inputs, and alter the response of the material depending on the identity of an applied signal.

Two birds with one stone: Two classical antiaromatic molecules, cyclobutadiene and pentalene, were stabilized by introducing one metal fragment by a [2+2] cycloaddition reaction of osmapentalyne with alkynes. These metalla-aromatic molecules absorb broadly from the UV to the near-IR region and show significant photoacoustic and photothermal effects.

Start to finish: A recently reported Pd0-catalyzed asymmetric Nazarov-type cyclization was applied in the key step of the first catalytic asymmetric total synthesis of (−)-rocaglamide (natural) and (+)-rocaglamide. The stereochemistry at the C3 position controls the stereochemistry of all other stereocenters and is determined in the cyclization step. dba=dibenzylidene acetone.

Boosting HER activity by phosphorus modification of tungsten nitride/reduced graphene oxide leads to a low-cost, high-performance, non-noble metal electrocatalyst for the hydrogen evolution reaction. The catalyst has a very small onset overpotential, a low Tafel slope, a large exchange current density in acid, and was stable in accelerated durability testing.

Fox in a box: New derivatives created from 1-diamino-2, 2-dinitroethene (FOX-7) often have properties superior to those of RDX. The compounds exhibit good thermal stability, high density, positive heats of formation, an acceptable oxygen balance, and excellent detonation properties. These findings contribute to the value of FOX-7 as an energetic precursor.

Crystallization-induced diastereoselective transformation of an α-methyl nitrile completes an entirely non-chromatographic synthesis of the halichondrin B C14–C26 stereochemical array. All four stereogenic centers in the Halaven C14–C26 fragment were assembled on a crystalline polycyclic template derived from the single chiral source D-quinic acid.

Flu finder: An electrochemical assay has been developed for the detection of influenza viruses using glucose-bearing substrates (SG1). By monitoring the release of glucose upon introduction of the virus, 19 different influenza strains have been successfully detected. The assay can also be used to rapidly measure drug susceptibility.

Golden sunshine: With 1-iodoalkynes as radical alkynylation reagents, unactivated tertiary aliphatic amines react in the presence of [Au2(μ-dppm)2]2+ (dppm=bis(diphenylphosphanyl)methane) in sunlight to afford propargylamines. A CC coupling of an α-aminoalkyl radical and an alkynyl radical was proposed as the mechanism.

Freezing-induced mechanochemistry: A new diarylbibenzofuranone-based mechanophore showed reversible color change by external forces through radical mechanism. By incorporating the mechanophore into polymer chains, it was revealed that freezing gels induced mechanical force along the chains, but the force was not large enough to cleave usual covalent bonds.

The direct aldol reaction of an α-azido 7-azaindolinylamide is promoted by a Cu-based catalyst. Aromatic aldehydes bearing an ortho substituent exhibited diastereodivergency depending on the nature of the chiral ligands used. A vicinal azido alcohol unit led to the corresponding aziridine, and facile hydrolysis of the 7-azaindolinylamide moiety furnished enantioenriched β-hydroxy-α-azido carboxylic acid derivatives.

Put a ring on it: The insertion of two benzene moieties at the meso positions of a porphycene framework yields meso-dibenzoporphycene (mDBPc). The compound has a small electrochemical HOMO–LUMO gap (0.81 eV) and an NIR absorption band at 1047 nm. X-ray photoelectron spectroscopy and a theoretical study indicate that, unusually for a porphycene derivative, the cis tautomeric form of the porphycene framework is more stable than the trans form.

The hunt for high energy: Derivatives of 4,4′-bis(5-nitro-1,2,3-2H-triazole) were synthesized by different functionalization strategies. Competitive detonation properties were achieved and compared to reported analogues of fully carbon-nitrated bis(azole) compounds.

Supramolecular octopus couples form when a positively quadrupolar cyclic AgI–triazolate trimer with fluorous octopus arms electrostatically attracts a negatively quadrupolar free porphyrin or a PtII porphyrin with shorter alkyl octopus arms. In their Communication (DOI: 10.1002/anie.201411462), C. Yang, M. A. Omary et al. show that in this system, the phosphorescence of the PtII porphyrin is enhanced under ambient conditions as O2 and self-quenching processes are suppressed.

That’s great, DEER! When a double-histidine Cu2+-binding motif (shown in blue) assembled in situ from natural amino acid residues and a metal salt was used as a rigid spin probe for double electron–electron resonance (DEER) distance measurements, dramatically narrower and readily interpretable distance distributions were observed than with a commonly used flexible spin label (red). Molecular modeling of an unlabeled protein gave a distance within 0.5 Å of the experimental value.

Power trip: A perylene dye derived from N-annulated thienocyclopentaperylene, which is characterized by a low-energy gap and a high electron injection yield, was synthesized for dye-sensitized solar cells. A high power conversion efficiency of 12 %, at an irradiance of the AM1.5G sunlight, was achieved. This efficiency is the highest achieved thus far by using just a metal-free organic dye.

Acenes eleven: A highly soluble pyrene-fused undecacene is prepared by adding end-capping triptycenylene units to the linear π system (see structure, N blue). The new compound shows a high tendency to crystallize; two polymorphs from dichlorobenzene and chloroform solutions could be obtained.

Without a trace… A highly stereoselective cycloaddition strategy provided efficient access to a diverse array of 5-unsubstituted pyrrolidines and enabled a five-step total synthesis of isoretronecanol (see scheme). A novel role of sodium borohydride in reductive decyanation was observed.

No chip off the old block: A multifunctional platform was developed for the simultaneous capture, sensing by surface-enhanced Raman scattering (SERS), and inactivation of bacteria (see picture). The SERS chip featured excellent reproducibility, good bacterial-capture efficiency, high sensitivity, and a high antibacterial rate, and was found to be suitable for capturing and discriminating bacteria in real systems.

Like dancers on ice who make pirouettes, dipolar molecular rotors have been programmed to spin in mesoporous fluorinated organosilica materials. In their Communication (DOI: 10.1002/anie.201412412), A. Comotti, P. Sozzani, et al. report on the fast reorientation of the carbon–fluorine dipole. The relaxation rates obtained by NMR spectroscopy were modulated by the dipole dynamics, which in turn were regulated by I2 vapor entering the pores.

Obituaries

Carl Djerassi died at the age of 91 on January 30, 2015. He is best known for developing the synthetic hormone used to the present day in the oral contraceptive commonly known as The Pill. Djerassi’s other achievements include the use of mass spectrometry in organic chemistry, and extensive research on antibiotics and marine natural products. He was also an author of plays, poems, and short stories, including Oxygen, written together with Roald Hoffmann.

Crystal clear: Molecular dynamics simulations uncover the nuclei breeding factory responsible for secondary nucleation in crystal growth. The question why a few crystal seeds give rise to a many-fold increase in new crystals is answered. This mechanistic insight will enable better control in engineering crystalline products to design.

Without a metal: A large variety of N-heterocycles and boronates were subjected to the title reactions, which proceeded with high efficiency and excellent regio- and enantioselectivity. The new method was applied in complex molecule synthesis.

One way or another: A strategy has been developed for the assembly of DNA nanocages that can not be assembled directly. In this approach a precursor DNA nanocage is assembled first and is then isothermally transformed into a desired, complicated nanocage. Dramatic changes in the 3D structures and topologies accompany the transformation, as shown by native polyacrylamide gel electrophoresis and cryogenic electron microscopy imaging.

A heart of gold: Gold nanocluster [Au23(PhCC)9(Ph3P)6]2+ has an unprecedented Au17 kernel protected by three PhC2-Au-C2(Ph)-Au-C2Ph motifs (see picture; green, yellow, and red) and six Ph3P units. DFT electronic structure analysis suggests that the stability of the 12-electron cluster is due to the splitting of the superatomic 1D orbitals under the D3h symmetry of the Au17 core. Atom colors: Au=orange/blue; P=purple; C=gray.

The superstructure of a substituted zeolitic imidazolate metal–organic framework was determined from a combination of experimental NMR chemical shifts and DFT-calculated shifts (see picture). The study indicates the presence of two different environments for each type of functional group in the metal–organic framework.

Reversible encryption: Dynamic materials for regulation of cell adhesion are important to a variety of biological and biomedical applications. This study demonstrates an encrypted ligand and hydrogel with the capability of inducing and inhibiting cell adhesion, which is controlled by hybridization reaction-driven molecular reconfiguration. U=unblocking sequence, R=recovering sequence.

Catch and release: Multifunctional capture reagents were developed that enable enzymatically-triggered release and direct detection of lipid-modified peptides by mass spectrometry. Dynamic proteome lipidation was visualized, enriched, and identified on an unprecedented scale, both in cells and in a developing zebrafish embryo.

C3B or not C3B that is the question—Previous theoretical predictions suggest that the stoichiometrically doped graphite C3B should be a promising H2- and Li-storage material, with potentially important applications in power storage. The first experimental measurements of the real material indicate, however, that disorder is a limiting factor for the use of C3B as an energy storage material.

An active family: A quassinoid with a unique cagelike 2,4-dioxaadamantane ring system (see structure) was isolated along with biosynthetically related quassinoids from the twigs and stem of Harrisonia perforata. The compounds demonstrated insecticidal activity, antagonist activity at the nicotinic acetylcholine receptor of insects, and potent cytotoxicity. Their discovery provides an alternative origin of the quassinoid family of compounds.

Switching the water adsorption mode on TiO2 to dual H-bonding by the presence of fluorine atoms at the surface not only thermodynamically enables the hole transfer to the water molecules, but also facilitates the proton-coupled electron transfer during water oxidation. This phenomenon is established by IR spectroscopy studies and calculations.

Electron bridge: An efficient strategy for improving the electron transfer between radicals and enolates has been developed. A redox-active copper species activates the free radical and brings the radical and enolate within proximity, which in turn facilitates the electron transfer. Thus, a cascade reaction for the synthesis of highly functionalized pyrrolidine-2,5-diones was developed.

Sele-C-C-tivity! Highly selective CC bond cleavage of model compounds for the lignin β-O-4 linkage was promoted by a catalyst formed in situ from [Ru(Cl)(H)(PPh3)3] and the ligand triphos (see scheme). Mechanistic investigations indicated a hydrogen-transfer-based retro-aldol pathway for this transformation.

Azo borealis: The first 1,2-azaborinine-substituted azo dyes have been synthesized using sterically demanding boroles and organic azides. The ring-expansion mechanism of the unexpected formation of the bright yellow chromophores was investigated by DFT calculations.

The analogy goes further: Following the often-studied donor–acceptor-substituted cyclopropanes, the corresponding cyclobutane derivatives were employed for the ring-strain-driven stereoselective syntheses of carbo- and heterocycles.

An asymmetric cross-hydroalkenylation catalyzed by [NiH] complexes provides branched gem-disubstituted olefins with high enantio- and chemoselectivity, depending on the steric and electronic effects of the substrates and N-heterocyclic carbene (NHC) ligands. In their Communication (DOI: 10.1002/anie.201411882), C.-Y. Ho and co-workers rule out a π,π-stacking mechanism and suggest that the N-aryl rings of the NHCs possibly “move like wings” by coordinating a π system with NiII.

Making one into two: Palladium-catalyzed direct C(sp3)H activation of an N-allyl imine led to the generation of an all-carbon π-allyl complex which presumably remains in equilibrium with a rare 2-aza π-allyl species. Nucleophilic attack on the π-allyl intermediates gave either a 1-aza-1,3-diene or 2-aza-1,3-diene in a completely regioselective manner.

Out for the count: The unusual stability and reconstruction of surface cobalt and nickel carbides containing square-planar carbon atoms is explained by local aromaticity and electron count. A chemical bonding model for these systems is presented and explains the unusual structure, special stability, and the reconstruction. Several new aromatic and stable two-dimensional alloys are predicted.

Ether way: Two new sesquiterpene ethers were obtained by incubation of farnesyl diphosphate with a recombinant terpene cyclase from Kitasatospora setae. The structures of both terpenes were elucidated by NMR spectroscopic methods. Incubation experiments with isotopically labeled precursors gave detailed insight into the mechanism of the bacterial sesquiterpene cyclase.

Biphenol-type chiral phosphoric acids serve as co-catalysts to induce enantioselectivity in the palladium(II)-catalyzed oxidative carbocyclization–borylation of enallenes. The method was used to prepare a number of enantioenriched borylated carbocycles in high yields and enantioselectivities (up to 93 %). BQ=benzoquinone, pin=pinacolato.

Riding the wave of erbium SMMs: The first trigonal pyramidal mononuclear erbium(III) single-molecule magnet (SMM) was synthesized and its magnetic properties investigated. Despite containing an axial Cl− ligand, which is expected to reduce the prolate nature of the erbium(III) ion, the molecule exhibits out-of-phase signals in the ac susceptibility data in the absence of an external field and hysteresis behavior up to 3 K.

Overloaded: Porous molecular nanocontainers of the {Mo132} Keplerate type can integrate a uniquely large number of fluorides. These F− ions (see structure, green) are partly as coordinated ligands at both the {(MoVI)MoVI5O21(H2O)5(F)} pentagonal units (orange) and the linkers (blue), partly as a disordered water/fluoride assembly inside the cavity. The H2O ligands are shown as red spheres (larger red spheres are for H2O coordinated e.g. to the MoV centers of the linkers).

Selective switch: A dimeric BODIPY dye with reduced symmetry is ineffective as a photosensitizer unless it is activated by a reaction with intracellular glutathione (GSH). Staining with red-fluorescent Annexin V shows that the photosensitizer is preferentially switched on in cancer cells, which feature a higher GSH level than normal cells.

Aryl boronic acids can be monofluoromethylated under nickel catalysis. The utility of this method is demonstrated by the monofluoromethylation of a borylated and acyl-protected derivative of the statin drug ezetimibe. Mechanistic investigations indicate that a fluoromethyl radical is involved in the NiI/NiIII catalytic cycle.

Signal passing in DNA: A triggered self-assembly process of DNA nanostructured tiles is demonstrated. The DNA-strand-exchange mechanism sends a signal across a tile leading to a binding event by activation of a second binding site 18 nm away. Five unique DNA tiles self-assemble sequentially in a domino-like cascade.

Oxynitride solid: Solid bases, such as SBA-15-oxynitrides, have attracted considerable interest for potential applications as catalysts in important industrial processes. Reported here is that tuning the temperature of nitridation (ammonolysis) leads to enhanced catalytic activity of these solid bases. Detailed studies are discussed to explain this change in activity.

Difluoromethylation

A new reagent: The elusive chemical reagent CF2HCHN2 was generated in situ for the first time and further reacted with alkynes in a [3+2] cycloaddition reaction. This transformation constitutes a novel and efficient approach to agrochemically important difluoromethylated pyrazoles.

Reviews

Asymmetric Synthesis

Auspicious ligands: Sulfoxides with chirality at the sulfur atom have mainly been used as chiral auxiliaries for diastereoselective reactions and have only recently emerged as a versatile class of chiral ligands. In this Review, the development of chiral sulfoxide ligands for asymmetric catalysis is discussed, and metal–sulfoxide bonding and strategies for the synthesis of enantiopure sulfoxides are described.

Going to great lengths: The length of chiral supramolecular polymers was precisely controlled through varying the enantiomeric excess. The homochiral assembly favors fibrous growth whereas heterochiral assembly preferentially leads to nanoparticles. The stronger heterochiral bindings at the growing ends of fibers effectively terminate the elongation of the fibers.

Silicon stargazing: A new type of mechanistic probe is designed and evaluated. A cocktail of deuterium-labeled hydrosilanes provides a “silent” stereochemical relationship between the silicon atom and the probe’s backbone as the basis of the analysis. This technique does not suffer from the biases of traditional methods, nor does it require the determination of the absolute configuration.

The end is Ni: Over the past two decades, nickel-rich materials, have become highly promising candidates for high-energy cathode materials for lithium-ion batteries. This Review brings a new perspective to Ni-rich materials as well as providing a comprehensive account of recent progress and limits, and new utilization possibilities for these materials. ESS=energy storage systems, EV=electric vehicles, HEV=hybrid electric vehicles, Mobile=mobile appliances.

Bottle opener: SSZ-13 is a zeolite commercialized as a catalyst to remove nitrogen oxides (NOx). However, its long synthesis time is one of the biggest barriers to large-scale production. An ultrafast synthesis route now allows SSZ-13 to be synthesized in 10 min and thus facilitates continuous preparation of SSZ-13. The fast-synthesized SSZ-13 exhibits outstanding performance for the NOx removal.

An electron-accepting benzophosphole oxide is combined with an electron-donating aminophenyl group to form a fluorescent probe. A. Fukazawa, T. Higashiyama, S. Yamaguchi et al. show in their Communication (10.1002/anie.201500229) that the probe exhibits a fluorescence color change as a function of solvent polarity while retaining high fluorescence quantum yields. The molecule was used as an adipocyte dye and allowed a fluorescence-based discrimination of the polarity of subcellular components.

Essays

Bürgenstock Conference

The secret of success: This year the famous “Bürgenstock Conference” will take place for the 50th time. This conference has become internationally one of the, if not the, most highly regarded conference in chemistry, chemical biology, and physical chemistry. What are the success factors of this conference? These as well as a number of perhaps more hidden figures and facts are discussed.

Lock, stock, and barrel: A two-step “loading-locking” process has been developed to encapsulate target guest molecules in porous metal–organic frameworks (MOFs). In this approach, size-matching organic ligands are preselected and deliberately grafted onto open metal sites to lock the pores of the MOFs to prevent the leaching of guests. Rapid release of the encapsulated guests can be achieved by application of an external stimulus.

From fluorination to etherification: A method for the formation of alkyl aryl ethers directly from the corresponding alcohols and phenols with PhenoFluor has been developed. The reaction features a broad substrate scope, and substrates that are challenging for more conventional ether bond forming processes may be coupled. TMS=trimethylsilyl.

Versatile reactivity: A new type of borenium cation is reported in which a naphthyl bridge supports a strong PB interaction. Borenium reacts with H2 through side-on coordination of H2 to boron, heterolytic splitting, and concomitant cleavage of the BMes bond. The molecule also reacts with 3-hexyne through a syn 1,2-carboboration reaction. NTf2−=triflimide.

The origin of inflammation in cell culture is commonly obscured by paracrine and autocrine signaling. A small-molecule immunopotentiator was developed that tags cells and initiates inflammation of the tagged cells using light. BMDCs=bone-marrow-derived dendritic cells, TNF=tumor necrosis factor.

On target: The over-expression of a mannose-6-phosphate receptor was demonstrated in prostate tissues and cancer cell lines. This receptor was targeted with a mannose-6-phosphate analogue grafted onto the surface of mesoporous silica nanoparticles (MSNs). MSNs were efficient for cancer imaging and therapy, thus demonstrating the potential of M6PR targeting for prostate cancer theranostics.

Copper works! [(CAAC)CuCl] reacts with both NaBH4 and BH3NH3 to afford [(CAAC)CuBH4] as a thermally and air-stable complex. Both complexes efficiently promote the hydrolytic dehydrogenation of ammonia borane at room temperature, with a turnover frequency of up to 8400 mol molcat−1 h−1. In addition, these air-stable catalysts are readily recyclable. CAAC=cyclic (alkyl)(amino)carbene.

Zo Zelective: After the initial discovery that ruthenium alkylidene catalysts with cyclometalated NHC ligands could enable the Z-selective homodimerization of terminal olefins, research into forming more complex products containing internal Z-double bonds has moved at a fast pace. This Minireview serves as a guide for the use of these catalysts and similarly powerful Z-selective ruthenium catalysts for the formation of complex cross products with Z-olefins.

A bolt from the blue: A synthetic designer guanylate cyclase producing a blue-light-inducible surge of the second messenger cyclic guanosine monophosphate (cGMP) in mammalian cells was used as an erectile optogenetic stimulator (EROS). Blue-light-dependent penile erection associated with occasional ejaculation was triggered in male rats by simple illumination of EROS-transfected corpus cavernosum with a portable commercial light-therapy device.

Asymmetric behavior: Using model electrochemical cells based on two identical onion-like carbon electrodes and two different ionic-liquid electrolytes and their mixtures, it was shown that the asymmetric behavior of the electrolyte cation and anion toward the two electrodes (see picture) limits the operating potential window of the cell and therefore its energy density.

A hierarchical porous framework with interconnected micro- and mesopores (analogous to a tree root system) has a unique structural advantage for carbon capture. The larger mesopores can substantially increase the accessibility of the micropores to guest molecules through enhanced diffusion. In their Communication (DOI: 10.1002/anie.201500305), S. Dai and co-workers introduce a soft-chemistry synthetic strategy based on a Friedel—Crafts alkylation for the creation of such porous phenolic polymers.

An electrochemical method has been developed to selectively extract Ti from the MAX phase Ti2SC to give C/S nanolaminates composed predominantly of amorphous and some graphene-like nanoflakes. In their Communication (DOI: 10.1002/anie.201500110), Y. Gogotsi et al. demonstrate the C/S nanolaminates to be promising cathode candidates for Li/S batteries. They also show that it is possible to electrochemically selectively extract Ti from a number of other MAX phases to create a new class of “AX” phases, most of which should be nanolayered.

Efficiency drive: A series of copper(I) fluoroalkoxide complexes bearing N,N ligands have been prepared and structurally characterized. These well-defined complexes serve as efficient reagents for the fluoroalkoxylation of aryl and heteroaryl bromides to produce a wide range of trifluoroethyl, pentafluoropropyl, and tetrafluoropropyl (hetero)aryl ethers in good to excellent yields.

A guiding light: By the combination of a light-activated sulfur-chelated olefin-metathesis catalyst with a photocleavable bulky silyl protecting group, two orthogonal pathways enabled the selective synthesis of five- or six-membered heterocycles according to the order in which the starting material was irradiated with light of different wavelengths. Thus, protecting-group removal and metathesis gave either a dihydropyran or a dihydrofuran.

Chloroacetic acid promotes an efficient and diastereoselective intramolecular cascade reaction of electron-deficient ynenones to deliver products featuring a 2,3,5-trisubstituted furan bearing a fused cyclopropyl substituent at the 5-position. Synthetically relevant polycyclic building blocks featuring rings of various sizes and heteroatoms have been synthesized in high yield using this mild acid-catalyzed reaction.

I(003) is a double agent: A tandem CN and CC bond-forming reaction has been achieved through RhII/Pd0 catalysis. The sequence first involves an iodine(III) oxidant, then the in situ generated iodine(I) by-product is used as a coupling partner. The overall process affords complex building blocks with high yields, and demonstrates the synthetic value of iodoarenes produced in trivalent iodine reagent mediated oxidations.

Roll in, unroll: Peptide cargoes were fused to cell-penetrating peptides (CPPs) and cyclized through a disulfide bond. This cyclization increases their proteolytic stability and cell permeability. Once they enter the cell, the disulfide bond is reduced by intracellular thiols, thus leading to regeneration of the functional linear peptides.

Palladium binds H2: The first dihydrogen complex of palladium has been synthesized and characterized, employing a tBuPCP (κ3-2,6-(tBu2PCH2)2C6H3) pincer ligand. The complex is investigated by X-ray crystallography and NMR spectroscopy, which reveals a very short HH bond length.

Antigen cross-presentation is the uptake of exogenous antigens followed by processing in the MHC-I complex, which is normally reserved for endogenous antigens. This process may now be studied by using masked epitopes: Azides are exploited as bioorthogonal protecting groups to generate antigens that are not recognized by their cognate T-cell unless they are deprotected using an on-cell Staudinger reduction.

(Hetero)genius: A general method for the direct thiolation of electron-rich heteroarenes was developed by employing Pd/Al2O3, a recoverable and commercially available heterogeneous catalyst, and CuCl2. Preliminary mechanistic studies indicate a heterogeneous active catalytic species, with the two metals playing complementary roles in the formation of the thiolated products.

In one direction: Highly b-oriented MFI zeolite films have been successfully prepared for the first time under neutral conditions without the use of hydrogen fluoride. The Na2O species dissolved from the glass plate support or a trace amount of NaOH facilitates the secondary growth of MFI seed crystals.